TW412762B - Ceramic multilayer capacitor - Google Patents

Abstract

The invention relates to a ceramic multilayer capacitor comprising a number of ceramic layers on the basis of a doped (Ba, Ca)[Ti, Zr]O3 as well as a number of electrode layers of Ni, the ceramic layers and the electrode layers being alternately stacked to form a multilayer structure which is provided with electric connections at two side faces, said electric connections being connected to a number of the electrode layers. The invention is characterized in that the composition of the main component of the doped (Ba, Ca)[Ti, Zr]O3 corresponds to the formula (Ba<1-x>Ca<x>)(Ti1-a-b-c-yZryMnaMobAc)kO3-<delta> wherein: 0.00<=x<=0.05; 0.10<=y<=0.25; 0.00<a<=0.01; 0.00<b<=0.01; 0.00<=c<=0.01; 0.99<k<0.999 and wherein A stands for at least one element selected from the series consisting of Y, Ho, Dy, Er, Yb, Ga, Ni, Mg, Zn, and Al, the elements Y, Ga and Zn being preferred. The invention also relates to a ceramic composition of this kind as well as to a method for the manufacture of the above-mentioned ceramic multilayer capacitors. Multilayers capacitors in accordance with the invention have a very high lifetime, a high dielectric constant, a high insulation resistance and a suitable temperature characteristic. This applies especially if A stands for Y, Ga and/or Zn.

Description

412762 V. Description of the invention (1) The present invention relates to a ceramic multilayer capacitor including a multilayer ceramic layer with a doped (Ba, Ca) [Ti, Zr] 〇3 substrate and a multilayer electrode layer made of Ni. Both sides of a multilayer structure formed by overlapping layers and electrode layers have electrical connections 1 and the electrical connections reach a number of electrode layers. The invention also relates to ceramic materials suitable for use in ceramic multilayer capacitors. The present invention is more about a method of manufacturing a ceramic multilayer capacitor. Such ceramic multilayer capacitors are well known in the introduction. US Patent Documents Nos. 5, 3, 19, 5 1 7 are described in detail. The patent revealer, in more detail, is a multilayer capacitor whose doped (Ba, Ca, Sr) [Ti, Zr] 03 ceramic layer is the main matrix material. This material is the so-called mother titanite structure. 3 As far as this material is concerned, the quantitative Ca ions and Sr hammers replaced the position of Ba in the perovskite (the so-called A-position), and the quantitative Zr raccoon replaced Ή Location (so-called B-location). It is well known that the electrode layer of a capacitor is mainly made of N1. In the manufacturing process of capacitors, the doping materials include metals. Mn, rhenium, V, and W and / or compounds will be transformed into their oxide forms during firing and added to the burned and crushed (B a, C a, S r) [T i, Z r] 03 powder a In order to reduce the minimum sintering temperature of the ceramic material, a sintering aid can also be added = the sintering temperature must be quite low to avoid the Ni electrode layer in the sintering process There is a disadvantage of the well-known ceramic multilayer capacitors = the palm has found that, in practice, the performance of capacitors made according to the specified composition is not optimal. In particular, it has been proven that with the well-known capacitors, the requirements for improving the life of capacitors have never been achieved. An object of the present invention is to improve the above disadvantages. In more detail, this post

Page 7 412762 5. Description of the invention (2) The Ming system aims to propose a ceramic multilayer capacitor containing an electrode layer made of Ni. It has a long life, high dielectric constant, high insulation resistance, and ideal temperature. characteristic. The invention should also provide a ceramic material that can be made into a capacitor with a very long life, a very high dielectric constant, a very high insulation resistance, and ideal temperature characteristics. Still another object of the present invention is to provide a method for manufacturing a ceramic multilayer capacitor having a long life, a very high dielectric constant, a very high insulation resistance, and ideal temperature characteristics. These and other objects of the present invention are achieved by the ceramic multilayer capacitor mentioned in the introduction, and other characteristics are the main f component composition formula of doped type (Ba, Ca) [Ti, Zr] 03 as ( Bat ^ CaJCTi ^ a ^^ Zr ^ MObA ^ 'Ao where: 0. 0 0 SXS 0. 0 5 0.10 ^ y ^ 0.25 0.00 &lt; a S 0.01 0.00 &lt; b 0.01 0.00 ^ c ^ 0.01 0. 99 &lt; k &lt; 0.999 and A represents at least one element selected from the series consisting of Y, Ho, Dy, Er, Yb, Ga, Ni, Mg, Zn, and A 丨. Among many experimental results, 1 makes the present invention successful. Inventor

Page 8 412762 V. Description of the invention (3) The extremely fast accelerated life test (HALT) of the capacitor of the above type is now conducted to prove that the life is unexpectedly extended and the reliability is very high. Furthermore, it has been proved that the capacitor of the present invention has a high dielectric constant ε (15, 0.0 and higher), a relatively low loss factor (5% or lower), and a relatively high insulation resistance. The first set of experiments proved that the relationship between dielectric constant and temperature (temperature characteristics) meets the so-called Y5V standard of EI. The cause of the long life is still unknown. However, the inventors are convinced that the complex Mη-Μό complex is the main cause of this excellent effect. It is believed that such donor / acceptor-complexes can avoid the formation of so-called zero vacancies in the BaTi 03 structure of the grains of the dielectric material. It is known that the existence of such a 0-vacancy will reduce the insulation resistance of the dielectric material and greatly reduce the life of the ceramic multilayer capacitor. The donor / acceptor complexes mentioned above will form extremely strong stress centers, which will reduce the 0-vacancy mobility. The presence or absence of W and / or V has an adverse effect on the formation or existence of this complex, and as a result, as shown in US 5,319,51 7, the life span is greatly reduced.

The addition of a dopant substance to the BaT 1 03 crystal structure is necessary to make the material of the present invention suitable for use as a dielectric material in ceramic multilayer capacitors. In this example, the Ca ion occupies the Ba or M position, and the Z r, M η and Z r, M η, and N b ions occupy the T 1 or donor position in the BaT 1 03 material. Please note that the specified amount of the doping substance is calculated in terms of the amount of all effective Ba and T i positions in the material. The specified amount of C a stock at the B a position of the ceramic material is considered to be the main reason that makes the ceramic multilayer capacitor work well. The amount of C a widens the dielectric peak of the ceramic material. 3 The amount of Ca in the ceramic material exceeds 0.5 5

412762 V. Description of the invention (4) The dielectric number of the material is reduced to an extremely low value of 3, and further, if X &gt; 0. Q 5, the dielectric loss is severely beneficial = if the Ca content range at the Ba position in the ceramic material The weights of 0.03 and 0.04 5 are optimally adjusted between the small dielectric peaks to be avoided and the low dielectric constant due to high dielectric loss. The presence of Zr 1 Mn, Mo and element A in the specified amount at the T 1 position in the ceramic material is also considered as the main prerequisite for the good operation of ceramic multilayer capacitors. As for other doping substances, the presence of Zr causes the maximum value of the dielectric constant of BaT 103 to shift from the high temperature region of Fu. If the amount of Zr is lower than the portion of 0.1 or higher than the portion of 0.25, the Curie points are either too low or too high, respectively. This makes the dielectric constant of the material too low at operating temperature (room temperature). If the Zr amount range is between 0.17 and 0.22, the position of the Curie point is at the best point. Mη plays an important role in the sintering of the ceramic material of the multilayer capacitor according to the present invention. The sintering process is performed in a reducing gas. During the sintering process, β a T i 0 3 may be reduced. In this way, the resistance of the ceramic material made by the sintering method is greatly reduced, and the life of the multilayer capacitor is reduced. ‘This is the least desirable. * It has been proven in experiments that the presence of a certain amount of η at the Ti position in the ceramic material prevents the ceramic material from undesirably deteriorating its characteristics. The effectiveness of Mn can prevent the reduction phenomenon, especially in the crystal grains in the ceramic material. If the amount of M η contained in the ceramic material exceeds 0.0 丨, the dielectric constant is too low. The best conditions obtained between the desired characteristics are when the amount of Mη ranges between 0.02 and 0.06, so that the reduction of the sealing can be avoided and a high dielectric constant can be obtained = As mentioned above, the amount of Mo is also very important, especially for Mo and Mη.

Page 10 412762 V. Description of the invention (5) In terms of the formation of complex donor-receptor complexes. It is believed that these complexes are the reason why the multilayer capacitor of the present invention has a very long life. A very small amount of M0, that is, a portion of about 0.01 can extend the working life of the capacitor. It has been confirmed that the dielectric material tends to be more semiconductive if the amount of Mo in the material is far more than 0.01 parts. The preferred range of Mo amount is between 0. 0 2 and 0. 0 6 5 1 The purpose is to achieve the best combination between the high working life of the dielectric material and the undesired semiconducting properties . Note that the amount of Mo is preferably higher than the total amount of Mn and A. Preferably, the doped type (: 83, 〇 &amp;) [1'1,2] ^ 03 of the multilayer capacitor of the present invention also contains a small amount selected from the group consisting of y,} 1〇), and 1% Y b, One or more elements in the G a, N i, M g, Z η and A 1 芩 series. These elements have a fixed price. After the addition of these elements, the optimization of temperature characteristics, dielectric constant and other required characteristics can be achieved. 0 丨 的 份量。 However, the maximum amount of the total of these elements should be 0. 0 丨 的 份量. If the amount is more than 0.01 parts, the optimal amount of the undesired phase in the dielectric material will be in the range of 0.02 and 0.06. It has been found through experiments that, more specifically, the amount of Y, Ga, and / or Zn has a positive effect on the life of the multilayer capacitor of the present invention. The number of (replacement type) 1 atoms and (replacement type) Ba atoms in the calcium 'ore structure (k value is not equal to zero) varies, so the number of 0 atoms is not exactly 3. The amount of pseudo 3 in the formula is represented by (5. Because the number of acceptor atoms exceeds the number of donor atoms, the positions of the 0 atoms that should originally appear in the material are replaced by vacancies. • The present invention is Also about a doped (Ba, Ca) [Ti, Zr] 03 matrix

Page 11 412762 5. The novel ceramic composition of invention description (6). According to the present invention, the characteristic of this composition is that the composition formula of the main ingredients is (Ba ,. ττγ \ foaMobAc) k03-5 where * 0.00 ^ X 0.05 0.10 ^ y 0.25 0.00 &lt; a 0.01 0.00 &lt; b 0.01 0.00 ^ c 0 01 0. 99 &lt; k &lt; 0.999 and where A represents iii ΐ contains Y, Ho, Dy Ϊ Er &gt; Yb 5 Ga, Ni, Mg j Zn, and at least one element in the series A i. Ceramic composition can make excellent ceramic capacity σσ j, especially ceramic multilayer capacitor state containing Nim clothing electrode layer ° The metal content of this electrode layer is 5 less 9 0 wt% ^ The better is at least 9 8 \ 0% based on the above-mentioned principle 1 is also best to use the following formula = 0, .0 3 ^ X &lt;;0.45; 0. 17 ^ y ^ 0.22; 0. 0 0 2 &lt; a ^ 0. 0 0 6; 0. 0 0 2 &lt; b ^ 0. 0 0 6 5; 0. 0 0 2 Sc S 0. 0 0 6 and 0.9 9 &lt; k &lt; 0, 9 9 9. A preferred case is that A represents Y, G'a, and or Zn a. The present invention also relates to a method for manufacturing a ceramic multilayer capacitor, in which a doped (Ba, Ca) [Ti, Zγ] 03-based ceramic thin film is based on The screen printing electrode layer with Ni as the main component is covered, and then the ceramic layer and the electrode layer are alternately stacked.

Page 12 412762 5. Description of the invention (formed) to form a multilayer structure, then calcined and sintered in a reducing atmosphere, and then electrically connect the multilayer structure, that is, to connect multiple electrode layers, its characteristics are heterotype (Ba, The composition of the main ingredients of Ca) [Ti, Zr] 03 is: (Ba xxCax) (Ti pa—b_c_yZryMnaMobAc) kO “where: 〇. 〇 0 S x S 〇. Ο 5 0.10 ^ y ^ 0.25 0.00 &lt; a ^ 0.01 0.00 &lt; b ^ 0.01 0. 00 Sc ^ 0.01 0. 99 &lt; k &lt; 0.999 and wherein A represents a member selected from the group consisting of Y, Ho, Dy, Er, Yb, Ga, Ni, M g, Z n And at least one element in the series of A 丨. As mentioned above, the multilayer capacitor according to the present invention has a very long life, a high dielectric constant, a high insulation resistance, and ideal temperature characteristics. Especially when A is Y, Ga and / or Zn are more applicable. The characteristics of the first preferred embodiment of the present invention are doped (Ba, Ca) [Ti, Zr] 03. The preparation is a mixed oxide and / or The carbonate of the metal is then calcined and ground the mixture. Doped (B a, C a) [Τ_ 1, Z r ϊ Ο 3 structure package Containing M a 'M 0 and if necessary, a doping substance A will be formed at the position of B during the calcination process. Therefore, the doping substance may have a uniform ytterbium distribution in the grains of the main component of the ceramic layer. Sintering aid Admiration

Page 13 412762 V. Description of the invention (8) It is better to use Si 02 'and the content in the mixture is preferably 0.1 to 丨. 0 wt%, because it will make the mixture have better sintering characteristics. . The characteristic of another preferred embodiment of the present invention is the doped type (B a, C a) [T i, Z r] 03 is prepared by the sol-gel method. In the examples, an organic solution of a colloidal suspension containing solid phase particles is first prepared. In this example, the organic solvent (e.g., ethanol) containing hydrated metal oxide particles is preferred. After a small amount of water is added (using mediconic acid or hydroxide as a catalyst), the metal burns the oxide to undergo hydration. Subsequent polycondensation becomes the desired doped type (Ba, Ca) [T 1, Zι ·] 03. This reaction is usually completed after increasing the temperature of the suspension. Finally, the solvent is removed, for example, the evaporation method = the doped type (B a, C a) [T i, Z r] 03 thus obtained shows the collision in the material and the most uniform distribution of the impurities These and other aspects of the invention can be seen at a glance with reference to the specific embodiments described below. The diagram is as follows: FIG. 1 is a diagrammatic sectional view of a capacitor according to the present invention. It should be noted that for clarity, the parts within the circle are not shown to scale. The multilayer capacitor shown in Fig. 1 according to the present invention is composed of a plurality of ceramic layers 1 having a doped type (B a, C a) [T 1, Z r] 03 as a matrix. Correct composition system (BahCaxXTik-bc-yZq.MnaMcvWOw 'Where 0.00 SxS 0.05; 0. 1 0 ^ y ^ 0. 2 5; 0. 0 &lt; a ^ 0. 0 1; 0. 0 &lt; b ^ 0. 01; 0. 0 0 0 ^ c S 0. 0 1 and 0.9 9 &lt; k &lt; 0.9 9 9, and wherein A represents a member selected from the group consisting of Υ, Η 〇, D y, E r, Y b, G at least one element in the series of a, Ni, Mg, Zη and A1.

Page 14 V. Description of the invention (9) The capacitor also includes a capacitor made mainly of Ni, which has an electrical connection on both sides of 3 '. These connections contain a solder, which is the same as the screen printing method, and the film printed with a lot of screen printing can be stacked, followed by an electrode layer and a g-arm electrode layer 2 = In addition capacitor ^ Located on opposite sides of the capacitor, such as copper. In practice, the electrode layer f is on a ceramic thin film, and thereafter, they are completed. As shown in the figure, ceramic thin layers or other electrical connections are alternately connected for the sake of clarity.) Figure 1 shows only 6 layers of thunder poles. In practice, a 'multilayer capacitor' contains at least ten and at most hundreds of electrode layers. Their thickness is generally between about 0.5 to 2.0 microns. Tao Shi n n a ^ ^ "The thickness of the tile tie is generally between 2 and 20 microns = in practice" The capacitor is stacked on top and bottom of the screen-printed film plus a -layer cover layer 4. The covering layer is generally composed of a multi-layered non-screen printed ceramic film 'and the screen-printed film is sandwiched into the stack during the stacking process. Using the conventional oxide / carbonate method (the first method) or the sol ~ gel method (the two methods) is the third method. In the first method, the preparation of the powder mixture is required for the quantitative determination of the specified composition. Metal oxides and / or carbon salts are obtained by mixing. In order to prepare the ceramic material of the present invention, the starting materials for mining are as follows:

BaCo: 3 (SABED), CaC03 (Merck ρ · a.), Ti〇2 (FUji),

Zr02 (Mel), MnC03 (Baker), M〇03 (Merck), a 120, (Merck),

Ga3 03 (Merck- Schuchardt) j (CH3COOH), Mg. 4H, 0 (Mer ck) 1 N i 0, Y2 03 (S ΐ arck), Z n (i \ lerck), and R E2 〇3 (re represents E r, D y,

苐 Page 15 412762 V. Description of the invention CIO) 〇 〇 and Y b; A u e r-Re m y). The average grain size of the starting material is less than 1 micron3. Therefore, the obtained powder mixture is suspended in an aqueous solution, and a small amount of dispersant 1 is added to the suspension. The suspension is ground by a Zr02 ball mill for 24 hours. The average particle size of the powder is low. Below 0.4 microns. Next, the powder was dried in the air and maintained at a temperature of 11000 to 1250 ° C, and then calcined. X-ray diffraction scoliosis shows that this method achieves the desired, single-phase, doped material with perovskite structure according to the present invention. In the second method, 3 parts of tetrabutyl titanate (TBT-Ti (CH4H90) 4) and tetrabutyl zirconate (TBE-Zr (CH4Hg0) 4) are dried in 17 parts (= anhydrous). Dilute with isopropyl alcohol (C3 Η7 0 Η). The two alcohol mixtures were stirred for three hours while avoiding contact with water. According to the required Ba / Zr ratio, mix the two solution parts and stir for another three hours, avoiding contact with water. The resulting mixture was diluted with pure (anhydrous) acetic acid (CH3C00H) at 0.15 v 0.1. The sol obtained is therefore water sensitive, but can also be easily stored at room temperature for more than a month under dry argon. Anhydrous B a -acid M, C a -acetate, Mu -acetic acid H, heptanoate acid, and ^ or more kinds of acid of the non-A acid King set mixed Xinsuowan sister into 3 acetate The mixture was stirred in acetic acid and water (salt / acetic acid / water = 1/8/7) and heated to the boiling point until a clear solution was obtained. Then, 丨 .01 to 丨 .10 10 moles of acid solution is mixed with the above-mentioned fixed ratio solution. Finally, the mixing field is stirred until the light is transmitted. 3 The acetate-sol mixture is dried and dispersed to obtain a gel powder.

Page 16 412762 V. Description of the invention (11) Remaining in the air 丨 0 5 0 ~ 1 1 0 Ot sintered to form a kind of crystalline calcium i-type ore type mixed crystal powder not sintered after 3 sintered The perovskite material (obtained by the first method or the second method) is then ground with the same ball mill for about 6 hours. Therefore, the average particle size of the obtained powder was less than 0.8 microns. Add a small amount of Si 02 colloid and a binding solution (PVA) to this powder. Then, a green ceramic film having a thickness of, for example, 40 micrometers is produced from the powder-binder mixture. Electrode layers are screen-printed on these films using well-known techniques. To achieve this, a screen printing paste containing metal particles containing N 1 as a main component is used. The metal content of this paste contains at least 9 0 \ v t% 1 and preferably at least 9 8 w t of Ni 3. The thickness of this non-sintered layer is about 2 micrometers. Next, the sized printed films are stacked. The thin films are stacked in such a manner that the electrode layers of the even and odd layers are slightly staggered from each other. The laminated film is pressed into a multi-layer structure at a high temperature (about 80 ° C) with a uniaxial high pressure (about 300 bar). The structure is then cut into a rod shape in one direction, and the other direction Cut perpendicular to the first direction) to form a single multilayer capacitor cell = these single systems are sintered under a reducing nitrogen gas containing argon in a nitrogen atmosphere of rhyme and water under the condition of about 1320 t. After sintering, all monomers were annealed (reoxidized) in a nitrogen atmosphere containing 02 for about 2 hours. Finally, the two opposite sides of the single layer of the multilayer capacitor are coated with an external copper connection by dip coating. These connections are made of a solderable NiSi alloy using the Giovanni strengthening method. Then the mechanical and electrical properties of the ceramic multilayer capacitor are measured. Many experiments have shown that a series of multilayer capacitors with doped BaT 103 as the matrix are made according to the methods discussed above. Master of different series of recipes.

苐 πPage 412762 5. The composition of the (12) part of the invention description is. 1 _ (Ba .. 9SCa〇.M) (Ti. 81Zr. ISMn. (^ Moq.〇025Y .. With 5) .. 5 2 -(Ba〇96Ca〇, 04) (Ti 〇, 31Zr0_ I3Mn〇005〇M〇0 〇〇25Y〇. 〇〇25) 〇 0995O3- 〇3. (Ba0. Evil Ca0. 04) (Ti0. 8025¾. isM% 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 〇 〇 3-0 (Ba0. g6CaM4) (Ti0.3IZr .. lsMn0. _Mo .. 0025H〇., 0 .5.) 0._q〇3--5 5 '(Ba0.sha Ca0.04) (Ti0.slZrQ.lsMn0.005QM〇0.0025Zn0.0025) 0. ¢ 99503-5 6. (Ba〇.g6Ca () 4) (TiQ. 81Zr0, lsMn: .0025M0 .. 2 and 0._) 0. 99.003-5 7. (Ba0 96Ca0_04) (Tio8l ^ r0.18 ^ n0. 0025 ^ ° 0. 00'25J ^ 0. 0050 ^ 0. 0990 ^ 3- 0 8. (Ba.g6Ca.04) (Ti0 slZr.18Mn.-ΰ025Mο0,0025Yb0 〇.50). Which. 〇3-—In these series, the measured (average) data is recorded as follows: Insulation resistance IR (1 09 ohms at 25 ° C and 100 V; measured after 1 minute), Curie temperature Tc (° C, measured before and after annealing), dielectric constant e and lifetime (HALT Environment; 1 40 t and 1 3V / μ /).! No IR Tc £ HALT 1. 22 11.8 / 1.6 18200 &gt; 80 2. 4 27.9 / 18.9 19600 &gt; 80 η IS 7.5 / 1.5 16700 &gt; 80 4 . 26 10.0 / 1.S 15900 &gt; 50 5. 11 15.5 / -1.9 18400 &gt; 70 6. 7 19.3 / 17.1 22600 &gt; 70 7. 17 16.7 / 11.3 18600 &gt; 50 1 8. 10 14.2 / -1.7 16600 &gt; 50

苐 Page 18

Claims (1)

412762 Case number 87119799 7 Mou? The scope of the patent claim for the month / today is a ceramic multilayer capacitor, which comprises a multilayer ceramic research society with doped (Ba, Ca) [Ti, Zr] 03 as a matrix and a multilayer electrode layer made of Ni. This ceramic layer It overlaps with the electrode layer to form a multilayer structure. It has electrical connections on both sides. The electrical connections are connected to many electrode layers. The composition of the main components of 03 'is equivalent to the following formula: (BahXCax) (T ib a-bc-yZryMnaMobAc) k〇3- 〇- where: 0.00 X 0. 05 0. 10 y 0. 25 0 · 00 &lt; a d 0. 01 0. 00 &lt; b 0. 01 0. 00 c 0. 01 0. 99 &lt; k &lt; 0. 999 and where A represents γ, h〇, Dy, Er, Yb , Ga, Ni, Mg, Zn and at least one element selected from the series of A1. 2. The ceramic multilayer capacitor according to item 1 of the patent application, characterized in that A represents Y 'Ga and / or Zn. 3, the plant type is doped (with ,.) [^, 21:] 〇3 as the matrix | 1 ridge, which is characterized in that the composition of the main component is equivalent to ZryMnaM〇bAc) k〇 O: \ 56 \ 50155.ptc Page 1 20〇〇.08.11. 〇2〇412762 _ Case No. 87119799 y? Year (sixth amendment, the scope of the patent application where: 0.00 X 0., 05 0.10 y 0., 25 0.00 &lt; a 0. , 01 0.00 &lt; b 0,, 01 0.00 c 0. 0.99 &lt; k &lt; 0.999 and where A stands for Y, 1〇, Dy, Er, Yb, Ga, Ni, Mg, Zn and A 1 At least one element selected in the series. 4. The ceramic composition according to item 3 of the scope of patent application, characterized in that A represents Y, G a and _ /, or Z η 0 5. — There are many kinds of ceramics. Layer capacitors A method in which the Tao Jingye with doped type (B a, Ca) [Ti, Zr] 03 as the matrix has a screen printing electrode layer mainly composed of Ni, and then the ceramic layer and the electrode layer are alternately stacked to form a kind of The multilayer structure is then calcined and sintered in a reducing atmosphere, and then the multilayer structure is electrically connected to the multilayer electrode layer, which is characterized by the main ingredients of doped type (Ba, Ca) [Ti, Zr] 03 The composition is equivalent to the following formula: (BabXCax) (Tiha_b—c_yZryMnaM obAc) k03_ where: 0 · 00 S X S 0. 05 0.10 ^ y ^ 0.25 0: \ 56V56155, ptc Page 2 2000.08.11.021 412762 Case No. 87119799 VI. Patent Application Range 0.00 &lt; a 0. 01 0 · 00 &lt; b 0, 01 0. 00 c 0, 01 0. 99 &lt; k &lt; 0. 999 And where A represents at least one selected from the series consisting of γ, H〇, Dy> £ r and A1-Yb 'Ga, Ni, Mg, Zn 6. According to the 5th aspect of the scope of the patent application, Y, Ga and / or Zn. 'It is characterized by A representing 7. According to the 5th or 6th of the scope of the patent application, Γ τ. 7 1 η 尨 i- 丄 negative method' is characterized by doping (3 '(^) [1'1,2 The 〇03 series is made by mixing oxides and / or carbonates of the metals used, and then calcining and grinding the mixture. 8. The method according to item 5 or 6 of the scope of patent application, characterized by doping 3, 〇3) [! '丨, 21 *] 03 was prepared by sol-gel method. 9 The method according to claim 5 or 6, characterized in that S i 02 is added to the mixture. ----- O: \ 56 \ 56155.ptc Page 3 2000.08.11.022